US7261779B2 - System, method, and apparatus for continuous synthesis of single-walled carbon nanotubes - Google Patents

System, method, and apparatus for continuous synthesis of single-walled carbon nanotubes Download PDF

Info

Publication number
US7261779B2
US7261779B2 US10/455,767 US45576703A US7261779B2 US 7261779 B2 US7261779 B2 US 7261779B2 US 45576703 A US45576703 A US 45576703A US 7261779 B2 US7261779 B2 US 7261779B2
Authority
US
United States
Prior art keywords
feedstock
plasma
carbon
reactor
region
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related, expires
Application number
US10/455,767
Other versions
US20040245088A1 (en
Inventor
Slade H. Gardner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lockheed Martin Corp
Original Assignee
Lockheed Martin Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lockheed Martin Corp filed Critical Lockheed Martin Corp
Priority to US10/455,767 priority Critical patent/US7261779B2/en
Assigned to LOCKHEED MARTIN CORPORATION reassignment LOCKHEED MARTIN CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GARDNER, SLADE H.
Assigned to LOCKHEED MARTIN CORPORATION reassignment LOCKHEED MARTIN CORPORATION RE-RECORD TO CORRECT THE ADDRESS OF THE ASSIGNEE, PREVIOUSLY RECORDED ON REEL 014161 FRAME 0642. Assignors: GARDNER, SLADE H.
Priority to PCT/US2004/017810 priority patent/WO2004108591A2/en
Priority to EP04754421.8A priority patent/EP1644287B1/en
Publication of US20040245088A1 publication Critical patent/US20040245088A1/en
Priority to US11/834,210 priority patent/US7763231B2/en
Application granted granted Critical
Publication of US7261779B2 publication Critical patent/US7261779B2/en
Expired - Fee Related legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/158Carbon nanotubes
    • C01B32/16Preparation
    • C01B32/162Preparation characterised by catalysts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/158Carbon nanotubes
    • C01B32/16Preparation
    • C01B32/164Preparation involving continuous processes
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0809Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes employing two or more electrodes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0837Details relating to the material of the electrodes
    • B01J2219/0839Carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873Materials to be treated
    • B01J2219/0879Solid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0894Processes carried out in the presence of a plasma
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0894Processes carried out in the presence of a plasma
    • B01J2219/0898Hot plasma
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00Structure or properties of carbon nanotubes
    • C01B2202/02Single-walled nanotubes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00Nanotechnology
    • Y10S977/70Nanostructure
    • Y10S977/734Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
    • Y10S977/742Carbon nanotubes, CNTs
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00Nanotechnology
    • Y10S977/70Nanostructure
    • Y10S977/734Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
    • Y10S977/742Carbon nanotubes, CNTs
    • Y10S977/75Single-walled
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00Nanotechnology
    • Y10S977/70Nanostructure
    • Y10S977/773Nanoparticle, i.e. structure having three dimensions of 100 nm or less
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00Nanotechnology
    • Y10S977/70Nanostructure
    • Y10S977/773Nanoparticle, i.e. structure having three dimensions of 100 nm or less
    • Y10S977/775Nanosized powder or flake, e.g. nanosized catalyst
    • Y10S977/777Metallic powder or flake

Definitions

  • the present invention relates in general to an improved process for manufacturing carbon nanotubes and, in particular, to an improved system, method, and apparatus for continuous synthesis of single-walled carbon nanotubes.
  • swcnt single-walled carbon nanotubes
  • CVD chemical vapor deposition
  • Some of these prior art processes have also combined plasma generation, thermal annealing, and the use of various transition metal catalyst supports with one of the three techniques. See, e.g., U.S. Pat. No. 6,451,175 to Lal; U.S. Pat. No. 6,422,450 to Zhou; U.S. Pat. No. 6,232,706 to Dai; and U.S. Pat. No. 6,221,330 to Moy.
  • the present invention comprises a system, method, and apparatus for producing carbon allotropes such as single-walled carbon nanotubes (swcnt) in a continuous manner.
  • One embodiment of the invention uses a three-step process of carbon plasma generation, plasma stabilization, and product spray deposition, all of which are scalable to large, industrial volume production levels.
  • the plasma may be generated in several continuous manners, including electrical resistance heating and/or electron beam vaporization of feedstock, and catalytic pyrolysis of organic precursors.
  • the plasma is stabilized, for example, with radio frequency energy from inductance coils.
  • a transition metal catalyst and associated required catalyst support are used to form the end product of swcnt.
  • One advantage and application of the present invention is the continuous, large scale production of single wall carbon nanotubes for manufacturing high performance structures.
  • This method is superior to prior art processes because it provides for (i.) the continuous generation of carbon plasma, (ii.) stabilization of the carbon plasma for homogenization of the reactant mixture and transport of a high concentration of carbon plasma to the product formation zone, and (iii.) a continuous operation, flow-through reactor design.
  • the entire apparatus is designed so that it can be mounted vertically, such that continuous deposition of product can be precisely applied to a structure using an overhead robotic arm.
  • the initiation of the carbon plasma may be accomplished by several methods.
  • One option is vaporization of a resistively-heated graphite element to create a thermal plasma.
  • Carbon or graphite feedstock which are readily available from commercial suppliers as rod stock, fiber, or in a special-designed geometry, is continuously fed over two oppositely-charged electrodes. Low voltage, high current, electric power is then passed through the feedstock. This results in rapid resistance-heating of the feedstock.
  • the electric power is regulated by feedback control from an ultra-high temperature pyrometer, which measures the element temperature in order to maintain a peak temperature of around 3000° C.
  • the reactor is closed and sealed with a reduced pressure inert atmosphere of continuously-flowing inert gas.
  • Another method for generating the carbon plasma is to vaporize the feedstock with an electron beam.
  • This method uses an e-beam focused on, for example, a graphite feedstock to generate a carbon plasma. This design allows localized directional control of the energy and efficient energy transfer because of the highly conductive nature of the graphite.
  • Another method for generating the carbon plasma is catalytic pyrolysis of organic precursors. This is accomplished using a continuous feed of hydrocarbons in an inert gas stream through a heated zone or by passing through a plasma jet.
  • the heated zone can be accomplished using a device like a tube furnace or a tungsten coil.
  • the plasma jet can be accomplished using a cathode/anode plasma gun using a high voltage discharge to dissociate and ionize the hydrocarbon feedstock.
  • the second step in the process of the present invention is plasma stabilization.
  • Classical chemical engineering reactor design specifies that reactants should form a homogeneous mixture for optimization of product yield, purity, and reaction rate.
  • the stabilization step has been completely ignored in the processes reported in the open literature to date.
  • This stabilization step homogenizes the plasma energy density and concentration, leading to a more efficient reactor.
  • the stabilization of the carbon plasma is achieved using inductively coupled radio frequency (rf) energy or microwave (mw) energy from a wave guide.
  • the power and frequency are controlled such that the carbon plasma remains stable in the vapor phase.
  • Electrical resistance heaters also can be added inside the reactor to maintain a chamber temperature of up to 1700° C. This additional thermal energy may be used to reduce the required rf or mw energy needed to stabilize the carbon plasma, and to also promote a higher concentration of carbon vapor in the reactor. Stabilization of the plasma occurs immediately downstream from the generated plasma.
  • the third and last stage of the reactor is the swcnt formation zone.
  • One of the important elements of the formation zone is a transition metal catalyst and associated catalyst support.
  • the formation zone may have variations of geometry and supporting equipment that will affect the rate and purity of the swcnt production.
  • the formation zone is immediately downstream from the plasma stabilization zone.
  • One of the simplest designs for the swcnt formation zone is to transport the stabilized plasma through a catalyst screen in the deposition nozzle.
  • the catalyst screen can be made from a variety of materials, depending upon the operating temperature of the stabilization zone.
  • Some of these materials include ceramic fiber mesh with a transition metallic catalyst coating, a metallic screen made directly from the transition metallic catalyst, a carbon fiber coated with a transition metallic catalyst, and/or a porous silica membrane with a transition metallic catalyst deposited on the “exit” side of the membrane.
  • the flow rate, carbon concentration, pressure, and temperature should be carefully regulated. Differential pressure is used to push the swcnt product out the exit port.
  • Another method is to introduce the transition metal catalyst into the formation zone as a gas phase organometallic compound or as metal nanoparticles. In this manner, the formation of swcnt occurs in the flowing reactant stream and can be ejected for deposition on a surface. Yet another method is to coat a substrate with a transition metal catalyst and allow the formation zone to occur just on the outside of the reactor on the substrate.
  • FIGS. 1 a and 1 b are sectional diagrams of one embodiment of a system, method, and apparatus for continuous synthesis of single-walled carbon nanotubes, and is constructed in accordance with the present invention.
  • FIG. 2 is an isometric diagram of another embodiment of a system, method, and apparatus for continuous synthesis of single-walled carbon nanotubes, and is constructed in accordance with the present invention.
  • FIG. 3 is schematic isometric view of the system, method, and apparatus of FIG. 2 mounted to a robotic arm for one application, and is constructed in accordance with the present invention.
  • FIG. 4 is an isometric view of the system, method, and apparatus of FIG. 2 , and is constructed in accordance with the present invention.
  • FIG. 5 is schematic isometric view of the system, method, and apparatus of FIG. 2 mounted to a robotic arm for use in a manufacturing operation, and is constructed in accordance with the present invention.
  • FIG. 6 is a schematic diagram of an alternate embodiment of a system and process for continuous synthesis of single-walled carbon nanotubes constructed in accordance with the present invention.
  • FIG. 7 is a schematic diagram of another alternate embodiment of a system and process for continuous synthesis of single-walled carbon nanotubes constructed in accordance with the present invention.
  • FIG. 8 is a schematic diagram of another alternate embodiment of a system and process for continuous synthesis of single-walled carbon nanotubes constructed in accordance with the present invention.
  • FIGS. 1-8 a system, method, and apparatus for producing single-walled carbon nanotubes (swcnt) in a continuous manner is shown.
  • some of the embodiments of the present invention use a three-step process of carbon plasma generation, plasma stabilization, and product deposition, all of which are scalable to large, industrial volume production levels.
  • FIGS. 1 a and 1 b depict one embodiment of an apparatus 11 for producing single-walled carbon nanotubes.
  • Apparatus 11 comprises a continuous operation, flow-through reactor 13 having an initial region 15 ( FIG. 1 b ), a plasma stabilization region 17 , and a product formation region 19 .
  • the product formation region 19 is located immediately downstream from the plasma stabilization region 17 .
  • a feedstock 21 is located in the initial region 15 and is designed and adapted to be continuously supplied to the reactor 13 .
  • the feedstock 21 may comprise many different types and forms of material, but is preferably a carbon or graphite fiber feedstock, graphite electrodes, and may be supplied in the form of rod stock or fiber, for example.
  • Each of the embodiments of the present invention includes means for generating a continuous stream of carbon plasma 22 from the feedstock 21 .
  • apparatus 11 utilizes an electrical resistance heater 23 to form the plasma 22 .
  • the electrical resistance heater 23 is mounted to the reactor 13 for passing low voltage, high current, electric power through the feedstock 21 over two oppositely-charged electrodes 24 , 25 , such that the feedstock 21 is rapidly resistance-heated.
  • the electric power is regulated by feedback control 27 from an ultra-high temperature pyrometer 29 for measuring a temperature of the feedstock 21 to maintain a peak temperature of approximately 3000° C.
  • the apparatus 111 has means for generating the plasma 122 that comprises an electron beam device 123 that vaporizes the feedstock 121 .
  • An electron beam is focused on a graphite target with sufficient energy and spot size to rapidly heat the graphite target, creating a thermal carbon plasma. Beam dithering and graphite feed rate is optimized to provide complete consumption of the feedstock.
  • apparatus 111 comprises a continuous operation, flow-through reactor 113 having an initial plasma generation region 113 , a plasma stabilization region 115 , and a product formation region 117 .
  • a feedstock 121 is continuously supplied to the plasma generation zone 113 for generating a continuous stream of carbon plasma 122 from the feedstock 121 .
  • the apparatus 111 further comprises a reduced pressure inert atmosphere of continuously-flowing gas through supply 133 .
  • Apparatus 111 also includes inductance coils 141 for stabilizing the carbon plasma in a vapor phase with radio frequency energy.
  • apparatus 111 further comprises optional electrical resistance heaters for applying thermal energy to reduce the radio frequency energy required to stabilize the carbon plasma, and to promote a higher concentration of carbon vapor in the reactor.
  • apparatus 111 includes a transition metal catalyst and an associated catalyst support 169 for forming a product 165 .
  • the transition metal catalyst and the associated catalyst support comprise a catalyst screen 169 in a deposition nozzle 171 .
  • the reactor 13 further comprises a reduced pressure inert atmosphere 31 of continuously-flowing gas through supply 33 .
  • the gas may comprise argon, helium, nitrogen, or other inert gases.
  • Control of a feed rate of the feedstock 21 , the pressure of the argon gas 31 , and the electric power level results in control of partial vaporization of the feedstock 21 to a level such that enough carbon remains to facilitate a continuous line feed, as shown.
  • As physical contact is required between the two electrodes 24 , 25 and some of the carbon feedstock is vaporized it is important to not vaporize all of the feedstock, thereby leaving sufficient material to provide continuous contact of the feedstock with the trailing and forward electrodes.
  • Apparatus 11 also includes inductance coils 41 mounted to the reactor 13 for stabilizing the carbon plasma 22 in a vapor phase in the plasma stabilization region 17 with radio frequency energy via controller 43 .
  • the carbon plasma is stabilized by controlling the power and a frequency of the radio frequency energy, such that the carbon plasma is stabilized for homogenization of a reactant mixture and transport of a high concentration of the carbon plasma to the product formation region 19 .
  • the apparatus 11 further comprises electrical resistance heaters 51 mounted to the reactor 13 for applying thermal energy inside the reactor 13 to maintain a reactor temperature of up to approximately 1700° C. In this way, the thermal energy reduces the radio frequency energy required to stabilize the carbon plasma 22 , and promotes a higher concentration of carbon vapor in the reactor 13 .
  • a transition metal catalyst 61 (see catalyst feed 61 a in FIG. 6 ) on an associated catalyst support 69 for forming a product 65 are used to spray deposit material.
  • swcnt are grown on the catalyst particles they are entrained downstream towards the exit port of the reactor. Individual swcnt filaments physically bond to each other through van der Waals attraction and form bundles of filaments. As the bundles increase in size, their mass increases and they are pulled from the catalyst support 69 from the force of the entrainment of the flow stream. The flow stream is directed towards a build surface 71 where the swcnt bundles are deposited. The flow rate, carbon concentration, pressure, flow rate, and temperature are carefully regulated.
  • the transition metal catalyst and the associated catalyst support comprise a catalyst screen 69 (see catalyst and support screen 69 b in FIG. 7 ) in a deposition nozzle.
  • the catalyst screen 69 is formed from a material that is selected based upon an operating temperature of the plasma stabilization region 17 .
  • the material used to form the catalyst screen 69 is selected from among, for example, ceramic fiber mesh with a transition metallic catalyst coating, a metallic screen made directly from the transition metal catalyst (see catalyst and support screen 69 b in FIG. 7 ), a carbon fiber coated with the transition metallic catalyst, or a porous silica membrane with the transition metallic catalyst deposited on an exit side of the membrane.
  • the present invention such as apparatus 111
  • a system 301 which comprises a robotic arm 303 for supporting and manipulating the apparatus 111 such that continuous deposition of the product is applied to a workpiece 305 during manufacturing and assembly thereof.
  • the apparatus 111 , robotic arm 303 , and workpiece 305 are located inside a pressure and atmosphere controlled chamber 307 .
  • apparatus 111 forms part of a system 501 and is mounted to robotic arm 503 for applying product directly to workpiece 505 during manufacturing and assembly thereof.
  • the present invention has several advantages including the ability to produce single-walled carbon nanotubes in a continuous manner.
  • the three-step process of the invention is scalable to large, industrial volume production levels.
  • the plasma may be generated in several ways, including electrical resistance heating and/or electron beam vaporization of feedstock.
  • the plasma is stabilized with radio frequency energy from inductance coils.
  • a transition metal catalyst and associated catalyst support are used to form the swcnt end product.
  • the present invention continuously produces large quantities of single wall carbon nanotubes.
  • This method is superior to prior art processes because it provides for the continuous generation of carbon plasma, stabilization of the carbon plasma for homogenization of the reactant mixture and transport of a high concentration of carbon plasma to the product formation zone, and a continuous operation, flow-through reactor design.
  • Controlling the feed rate of the feedstock, the pressure of the argon gas, and the electric power level, partial vaporization of the feedstock is controlled to a level such that the there is enough carbon remaining to allow a continuous line feed.
  • the feedstock is vaporized with an electron beam, localized directional control of the energy and efficient energy transfer are achieved because of the highly conductive nature of the graphite.
  • the second step of stabilization is much improved over the prior art.
  • the stabilization step homogenizes the plasma energy density and concentration, leading to a more efficient reactor.
  • the stabilization of the carbon plasma is achieved using radio frequency energy from inductance coils and, optionally, electrical resistance heaters inside the reactor to promote a higher concentration of carbon vapor in the reactor.
  • the entire apparatus is designed so that it can be mounted vertically such that continuous deposition of product can be applied with precision using an overhead robotic arm.
  • employing the apparatus of the present invention for manufacturing applications provides outstanding advantages over prior art devices and assembly techniques.
  • the apparatus can be used to provide direct manufacturing of unitized structures using “mix and pour” processing, such that no tooling, fixtures, or part assembly are required.
  • the elimination of these traditional assembly steps yields revolutionary performance.
  • an apparatus constructed in accordance with the present invention theoretically yields a 68 to 78% weight reduction for some aircraft unitized wing boxes.

Abstract

A process for producing single-walled carbon nanotubes in a continuous manner includes carbon plasma generation, plasma stabilization, and product deposition. The plasma is generated by electrical resistance heating or electron beam vaporization of feedstock. The plasma is stabilized with radio frequency energy from inductance coils and with electrical resistance heaters in the reactor. Stabilization homogenizes the plasma energy density and concentration, leading to a more efficient reactor. Finally, a transition metal catalyst and associated catalyst support are used to form the end product. The formation region may have variations of geometry and supporting equipment that will affect the rate and purity of the swcnt production. The formation region is immediately downstream from the plasma stabilization region. In addition, the entire apparatus is designed so that it can be mounted vertically such that continuous deposition of product can be applied with precision using an overhead robotic arm.

Description

This patent application is related to U.S. patent application Ser. No. 10/455,495, entitled, Pure Carbon Isotropic Alloy of Allotropic Forms of Carbon Including Single-Walled Carbon Nanotubes and Diamond-Like Carbon, which was filed concurrently herewith and is incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Technical Field
The present invention relates in general to an improved process for manufacturing carbon nanotubes and, in particular, to an improved system, method, and apparatus for continuous synthesis of single-walled carbon nanotubes.
2. Description of the Related Art
Currently, production of single-walled carbon nanotubes (swcnt) is substantially limited to an experimental or laboratory scale with the largest production rates being on the order of only grams per day. There are several different processes that are used for swcnt production, such as laser ablation methods, arc discharge methods, and chemical vapor deposition (CVD) methods. Some of these prior art processes have also combined plasma generation, thermal annealing, and the use of various transition metal catalyst supports with one of the three techniques. See, e.g., U.S. Pat. No. 6,451,175 to Lal; U.S. Pat. No. 6,422,450 to Zhou; U.S. Pat. No. 6,232,706 to Dai; and U.S. Pat. No. 6,221,330 to Moy.
There are a number of problems with these existing, prior art methods. Many of them are batch-type processes that are capable of producing product only once per cycle, rather than producing a continuous supply of end product which would be far more desirable. As a result, the rates of production are relatively low, with some methods generating only enough product to scarcely conduct laboratory testing on the end product. Consequently, it would be very difficult if not impossible to scale these methods up to industrial quantity production levels. The scalability of production methods is critical for many potential industrial applications for swcnt. A few examples include high performance structures manufacturers, such as those in military, aerospace, motorsports, marine, etc., fabrication businesses and, more generally, materials suppliers. The inability to make large quantities of swcnt affordable inherently limits their applications to uses as reinforcements for composites and the like. Unfortunately, swcnt-reinforced composites have a number of limitations themselves, including: fiber/matrix adhesion problems, strength limitations due to matrix design, and only providing incremental improvements in other areas of performance. Furthermore, some prior art methods of producing swcnt make a resultant product that is the relatively low in purity. Thus, an improved process for continuous production of a relatively pure form of swcnt would be highly desirable for many practical applications.
SUMMARY OF THE INVENTION
The present invention comprises a system, method, and apparatus for producing carbon allotropes such as single-walled carbon nanotubes (swcnt) in a continuous manner. One embodiment of the invention uses a three-step process of carbon plasma generation, plasma stabilization, and product spray deposition, all of which are scalable to large, industrial volume production levels. The plasma may be generated in several continuous manners, including electrical resistance heating and/or electron beam vaporization of feedstock, and catalytic pyrolysis of organic precursors. In the second step of the invention, the plasma is stabilized, for example, with radio frequency energy from inductance coils. In the final step of the invention, a transition metal catalyst and associated required catalyst support are used to form the end product of swcnt.
One advantage and application of the present invention is the continuous, large scale production of single wall carbon nanotubes for manufacturing high performance structures. This method is superior to prior art processes because it provides for (i.) the continuous generation of carbon plasma, (ii.) stabilization of the carbon plasma for homogenization of the reactant mixture and transport of a high concentration of carbon plasma to the product formation zone, and (iii.) a continuous operation, flow-through reactor design. In addition, the entire apparatus is designed so that it can be mounted vertically, such that continuous deposition of product can be precisely applied to a structure using an overhead robotic arm.
The initiation of the carbon plasma may be accomplished by several methods. One option is vaporization of a resistively-heated graphite element to create a thermal plasma. Carbon or graphite feedstock, which are readily available from commercial suppliers as rod stock, fiber, or in a special-designed geometry, is continuously fed over two oppositely-charged electrodes. Low voltage, high current, electric power is then passed through the feedstock. This results in rapid resistance-heating of the feedstock. The electric power is regulated by feedback control from an ultra-high temperature pyrometer, which measures the element temperature in order to maintain a peak temperature of around 3000° C. The reactor is closed and sealed with a reduced pressure inert atmosphere of continuously-flowing inert gas. By controlling the feed rate of the feedstock, the pressure of the inert gas, and the electric power level, partial vaporization of the feedstock is controlled to a level such that the there is enough carbon remaining to allow a continuous line feed.
Another method for generating the carbon plasma is to vaporize the feedstock with an electron beam. This method uses an e-beam focused on, for example, a graphite feedstock to generate a carbon plasma. This design allows localized directional control of the energy and efficient energy transfer because of the highly conductive nature of the graphite.
Another method for generating the carbon plasma is catalytic pyrolysis of organic precursors. This is accomplished using a continuous feed of hydrocarbons in an inert gas stream through a heated zone or by passing through a plasma jet. The heated zone can be accomplished using a device like a tube furnace or a tungsten coil. The plasma jet can be accomplished using a cathode/anode plasma gun using a high voltage discharge to dissociate and ionize the hydrocarbon feedstock.
The second step in the process of the present invention is plasma stabilization. Classical chemical engineering reactor design specifies that reactants should form a homogeneous mixture for optimization of product yield, purity, and reaction rate. The stabilization step has been completely ignored in the processes reported in the open literature to date. This stabilization step homogenizes the plasma energy density and concentration, leading to a more efficient reactor. The stabilization of the carbon plasma is achieved using inductively coupled radio frequency (rf) energy or microwave (mw) energy from a wave guide. The power and frequency are controlled such that the carbon plasma remains stable in the vapor phase. Electrical resistance heaters also can be added inside the reactor to maintain a chamber temperature of up to 1700° C. This additional thermal energy may be used to reduce the required rf or mw energy needed to stabilize the carbon plasma, and to also promote a higher concentration of carbon vapor in the reactor. Stabilization of the plasma occurs immediately downstream from the generated plasma.
The third and last stage of the reactor is the swcnt formation zone. One of the important elements of the formation zone is a transition metal catalyst and associated catalyst support. The formation zone may have variations of geometry and supporting equipment that will affect the rate and purity of the swcnt production. The formation zone is immediately downstream from the plasma stabilization zone. One of the simplest designs for the swcnt formation zone is to transport the stabilized plasma through a catalyst screen in the deposition nozzle. The catalyst screen can be made from a variety of materials, depending upon the operating temperature of the stabilization zone. Some of these materials include ceramic fiber mesh with a transition metallic catalyst coating, a metallic screen made directly from the transition metallic catalyst, a carbon fiber coated with a transition metallic catalyst, and/or a porous silica membrane with a transition metallic catalyst deposited on the “exit” side of the membrane. The flow rate, carbon concentration, pressure, and temperature should be carefully regulated. Differential pressure is used to push the swcnt product out the exit port.
Another method is to introduce the transition metal catalyst into the formation zone as a gas phase organometallic compound or as metal nanoparticles. In this manner, the formation of swcnt occurs in the flowing reactant stream and can be ejected for deposition on a surface. Yet another method is to coat a substrate with a transition metal catalyst and allow the formation zone to occur just on the outside of the reactor on the substrate.
The foregoing and other objects and advantages of the present invention will be apparent to those skilled in the art, in view of the following detailed description of the preferred embodiment of the present invention, taken in conjunction with the appended claims and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
So that the manner in which the features and advantages of the invention, as well as others which will become apparent, are attained and can be understood in more detail, more particular description of the invention briefly summarized above may be had by reference to the embodiment thereof which is illustrated in the appended drawings, which drawings form a part of this specification. It is to be noted, however, that the drawings illustrate only an embodiment of the invention and therefore are not to be considered limiting of its scope as the invention may admit to other equally effective embodiments.
FIGS. 1 a and 1 b are sectional diagrams of one embodiment of a system, method, and apparatus for continuous synthesis of single-walled carbon nanotubes, and is constructed in accordance with the present invention.
FIG. 2 is an isometric diagram of another embodiment of a system, method, and apparatus for continuous synthesis of single-walled carbon nanotubes, and is constructed in accordance with the present invention.
FIG. 3 is schematic isometric view of the system, method, and apparatus of FIG. 2 mounted to a robotic arm for one application, and is constructed in accordance with the present invention.
FIG. 4 is an isometric view of the system, method, and apparatus of FIG. 2, and is constructed in accordance with the present invention.
FIG. 5 is schematic isometric view of the system, method, and apparatus of FIG. 2 mounted to a robotic arm for use in a manufacturing operation, and is constructed in accordance with the present invention.
FIG. 6 is a schematic diagram of an alternate embodiment of a system and process for continuous synthesis of single-walled carbon nanotubes constructed in accordance with the present invention.
FIG. 7 is a schematic diagram of another alternate embodiment of a system and process for continuous synthesis of single-walled carbon nanotubes constructed in accordance with the present invention.
FIG. 8 is a schematic diagram of another alternate embodiment of a system and process for continuous synthesis of single-walled carbon nanotubes constructed in accordance with the present invention.
DETAILED DESCRIPTION OF AN ILLUSTRATIVE EMBODIMENT
Referring to FIGS. 1-8, a system, method, and apparatus for producing single-walled carbon nanotubes (swcnt) in a continuous manner is shown. As will be described in greater detail below, some of the embodiments of the present invention use a three-step process of carbon plasma generation, plasma stabilization, and product deposition, all of which are scalable to large, industrial volume production levels. For example, FIGS. 1 a and 1 b depict one embodiment of an apparatus 11 for producing single-walled carbon nanotubes. Apparatus 11 comprises a continuous operation, flow-through reactor 13 having an initial region 15 (FIG. 1 b), a plasma stabilization region 17, and a product formation region 19. The product formation region 19 is located immediately downstream from the plasma stabilization region 17. A feedstock 21 is located in the initial region 15 and is designed and adapted to be continuously supplied to the reactor 13. The feedstock 21 may comprise many different types and forms of material, but is preferably a carbon or graphite fiber feedstock, graphite electrodes, and may be supplied in the form of rod stock or fiber, for example.
Each of the embodiments of the present invention includes means for generating a continuous stream of carbon plasma 22 from the feedstock 21. In this particular embodiment, apparatus 11 utilizes an electrical resistance heater 23 to form the plasma 22. The electrical resistance heater 23 is mounted to the reactor 13 for passing low voltage, high current, electric power through the feedstock 21 over two oppositely-charged electrodes 24, 25, such that the feedstock 21 is rapidly resistance-heated. The electric power is regulated by feedback control 27 from an ultra-high temperature pyrometer 29 for measuring a temperature of the feedstock 21 to maintain a peak temperature of approximately 3000° C.
In one alternate embodiment of the present invention (FIG. 2), the apparatus 111 has means for generating the plasma 122 that comprises an electron beam device 123 that vaporizes the feedstock 121. An electron beam is focused on a graphite target with sufficient energy and spot size to rapidly heat the graphite target, creating a thermal carbon plasma. Beam dithering and graphite feed rate is optimized to provide complete consumption of the feedstock. Like apparatus 11, apparatus 111 comprises a continuous operation, flow-through reactor 113 having an initial plasma generation region 113, a plasma stabilization region 115, and a product formation region 117. A feedstock 121 is continuously supplied to the plasma generation zone 113 for generating a continuous stream of carbon plasma 122 from the feedstock 121. The apparatus 111 further comprises a reduced pressure inert atmosphere of continuously-flowing gas through supply 133. Apparatus 111 also includes inductance coils 141 for stabilizing the carbon plasma in a vapor phase with radio frequency energy.
In addition, the apparatus 111 further comprises optional electrical resistance heaters for applying thermal energy to reduce the radio frequency energy required to stabilize the carbon plasma, and to promote a higher concentration of carbon vapor in the reactor. As will be described in further detail below, apparatus 111 includes a transition metal catalyst and an associated catalyst support 169 for forming a product 165. The transition metal catalyst and the associated catalyst support comprise a catalyst screen 169 in a deposition nozzle 171.
Referring again to FIGS. 1 a and 1 b, the reactor 13 further comprises a reduced pressure inert atmosphere 31 of continuously-flowing gas through supply 33. The gas may comprise argon, helium, nitrogen, or other inert gases. Control of a feed rate of the feedstock 21, the pressure of the argon gas 31, and the electric power level results in control of partial vaporization of the feedstock 21 to a level such that enough carbon remains to facilitate a continuous line feed, as shown. As physical contact is required between the two electrodes 24, 25 and some of the carbon feedstock is vaporized, it is important to not vaporize all of the feedstock, thereby leaving sufficient material to provide continuous contact of the feedstock with the trailing and forward electrodes.
Apparatus 11 also includes inductance coils 41 mounted to the reactor 13 for stabilizing the carbon plasma 22 in a vapor phase in the plasma stabilization region 17 with radio frequency energy via controller 43. The carbon plasma is stabilized by controlling the power and a frequency of the radio frequency energy, such that the carbon plasma is stabilized for homogenization of a reactant mixture and transport of a high concentration of the carbon plasma to the product formation region 19. In addition, the apparatus 11 further comprises electrical resistance heaters 51 mounted to the reactor 13 for applying thermal energy inside the reactor 13 to maintain a reactor temperature of up to approximately 1700° C. In this way, the thermal energy reduces the radio frequency energy required to stabilize the carbon plasma 22, and promotes a higher concentration of carbon vapor in the reactor 13.
In the product formation region 19, a transition metal catalyst 61 (see catalyst feed 61 a in FIG. 6) on an associated catalyst support 69 for forming a product 65 are used to spray deposit material. As swcnt are grown on the catalyst particles they are entrained downstream towards the exit port of the reactor. Individual swcnt filaments physically bond to each other through van der Waals attraction and form bundles of filaments. As the bundles increase in size, their mass increases and they are pulled from the catalyst support 69 from the force of the entrainment of the flow stream. The flow stream is directed towards a build surface 71 where the swcnt bundles are deposited. The flow rate, carbon concentration, pressure, flow rate, and temperature are carefully regulated. Differential pressure is used to push the product 65 out the exit port. The transition metal catalyst and the associated catalyst support comprise a catalyst screen 69 (see catalyst and support screen 69 b in FIG. 7) in a deposition nozzle. The catalyst screen 69 is formed from a material that is selected based upon an operating temperature of the plasma stabilization region 17. The material used to form the catalyst screen 69 is selected from among, for example, ceramic fiber mesh with a transition metallic catalyst coating, a metallic screen made directly from the transition metal catalyst (see catalyst and support screen 69 b in FIG. 7), a carbon fiber coated with the transition metallic catalyst, or a porous silica membrane with the transition metallic catalyst deposited on an exit side of the membrane.
As shown in FIGS. 3 and 5, the present invention, such as apparatus 111, may be used as part of a system 301, which comprises a robotic arm 303 for supporting and manipulating the apparatus 111 such that continuous deposition of the product is applied to a workpiece 305 during manufacturing and assembly thereof. In FIG. 3, the apparatus 111, robotic arm 303, and workpiece 305 are located inside a pressure and atmosphere controlled chamber 307. In FIG. 5, apparatus 111 forms part of a system 501 and is mounted to robotic arm 503 for applying product directly to workpiece 505 during manufacturing and assembly thereof.
The present invention has several advantages including the ability to produce single-walled carbon nanotubes in a continuous manner. The three-step process of the invention is scalable to large, industrial volume production levels. In the first step of plasma generation, the plasma may be generated in several ways, including electrical resistance heating and/or electron beam vaporization of feedstock. In the second step of stabilization, the plasma is stabilized with radio frequency energy from inductance coils. In the final step, a transition metal catalyst and associated catalyst support are used to form the swcnt end product.
The present invention continuously produces large quantities of single wall carbon nanotubes. This method is superior to prior art processes because it provides for the continuous generation of carbon plasma, stabilization of the carbon plasma for homogenization of the reactant mixture and transport of a high concentration of carbon plasma to the product formation zone, and a continuous operation, flow-through reactor design. Controlling the feed rate of the feedstock, the pressure of the argon gas, and the electric power level, partial vaporization of the feedstock is controlled to a level such that the there is enough carbon remaining to allow a continuous line feed. Moreover, if the feedstock is vaporized with an electron beam, localized directional control of the energy and efficient energy transfer are achieved because of the highly conductive nature of the graphite. The second step of stabilization is much improved over the prior art. The stabilization step homogenizes the plasma energy density and concentration, leading to a more efficient reactor. The stabilization of the carbon plasma is achieved using radio frequency energy from inductance coils and, optionally, electrical resistance heaters inside the reactor to promote a higher concentration of carbon vapor in the reactor.
The entire apparatus is designed so that it can be mounted vertically such that continuous deposition of product can be applied with precision using an overhead robotic arm. In particular, employing the apparatus of the present invention for manufacturing applications provides outstanding advantages over prior art devices and assembly techniques. For example, the apparatus can be used to provide direct manufacturing of unitized structures using “mix and pour” processing, such that no tooling, fixtures, or part assembly are required. The elimination of these traditional assembly steps yields revolutionary performance. In one embodiment, an apparatus constructed in accordance with the present invention theoretically yields a 68 to 78% weight reduction for some aircraft unitized wing boxes.
While the invention has been shown or described in only some of its forms, it should be apparent to those skilled in the art that it is not so limited, but is susceptible to various changes without departing from the scope of the invention.

Claims (28)

1. A system for producing single-walled carbon nanotubes, comprising:
a continuous operation, flow-through reactor having an initial region, a plasma stabilization region, and a product formation region;
continuously supplying feedstock to the initial region of the reactor to generate a continuous stream of carbon plasma from the feedstock, the carbon plasma being formed by electrical resistance heating of the feedstock, comprising: continuously feeding the feedstock over two oppositely-charged electrodes while passing low voltage, high current, electric power through the feedstock, such that the feedstock is rapidly resistance-heated, the electric power being regulated by feedback control for measuring a temperature of the feedstock to maintain a peak temperature of approximately 3000° C.;
stabilizing the carbon plasma in a vapor phase in the plasma stabilization region with radio frequency energy by controlling a power and a frequency of the radio frequency energy, such that the carbon plasma is stabilized for homogenization of a reactant mixture and transport of a high concentration of the carbon plasma to the product formation region; and
forming a product by depositing the reactant mixture in the product formation region.
2. The system of claim 1, wherein the carbon plasma is stabilized with inductance coils.
3. The system of claim 1, further comprising applying thermal energy inside the reactor to maintain a reactor temperature of approximately 1700° C., such that the thermal energy reduces the radio frequency energy required to stabilize the carbon plasma, and promotes a higher concentration of carbon vapor in the reactor.
4. The system of claim 3, wherein the thermal heat is applied by electrical resistance heaters.
5. The system of claim 1, wherein the reactor has a reduced pressure inert atmosphere of continuously-flowing gas, and wherein control of a feed rate of the feedstock, the pressure of the gas, and the electric power level, results in control of partial vaporization of the feedstock to a level such that enough carbon remains to facilitate a continuous line feed.
6. The system of claim 1, wherein the product is formed by using a transition metal catalyst and an associated catalyst support in the product formation region.
7. The system of claim 1, wherein the feedstock is selected from the group consisting of carbon feedstock and a graphite element.
8. The system of claim 1, wherein the feedstock is selected from the group consisting of rod stock and fiber.
9. The system of claim 1, wherein the product formation region is located immediately downstream from the plasma stabilization region.
10. The system of claim 1, wherein the product is formed in the product formation region by transporting the stabilized plasma through a catalyst screen in a deposition nozzle, the catalyst screen being formed from a material that is selected based upon an operating temperature of the plasma stabilization region, wherein the material is selected from the group consisting of ceramic fiber mesh with a transition metallic catalyst coating, a metallic screen made directly from the transition metallic catalyst, a carbon fiber coated with the transition metallic catalyst, and a porous silica membrane with the transition metallic catalyst deposited on an exit side of the membrane.
11. The system of claim 1, further comprising a robotic arm for supporting and manipulating the reactor such that continuous deposition of the product is applied to a workpiece.
12. An apparatus for producing single-walled carbon nanotubes, comprising:
a continuous operation, flow-through reactor having an initial region, a plasma stabilization region, and a product formation region;
a feedstock located in the initial region, the feedstock being adapted to be continuously supplied to the reactor;
means for generating a continuous stream of carbon plasma from the feedstock, comprising electrical resistance heaters mounted to the reactor for passing low voltage, high current, electric power through the feedstock over two oppositely-charged electrodes, such that the feedstock is rapidly resistance-heated, and the electric power is regulated by feedback control from an ultra-high temperature pyrometer for measuring a temperature of the feedstock to maintain a peak temperature of approximately 3000° C.;
inductance coils mounted to the reactor for stabilizing the carbon plasma in a vapor phase in the plasma stabilization region with radio frequency energy by controlling a power and a frequency of the radio frequency energy, such that the carbon plasma is stabilized for homogenization of a reactant mixture and transport of a high concentration of the carbon plasma to the product formation region; and
a transition metal catalyst and an associated catalyst support for forming a product by depositing the reactant mixture in the product formation region.
13. The apparatus of claim 12, further comprising electrical resistance heaters mounted to the reactor for applying thermal energy inside the reactor to maintain a reactor temperature of approximately 1700° C., such that the thermal energy reduces the radio frequency energy required to stabilize the carbon plasma, and promotes a higher concentration of carbon vapor in the reactor.
14. The apparatus of claim 12, wherein the reactor further comprises a reduced pressure inert atmosphere of continuously-flowing argon gas, such that control of a feed rate of the feedstock, the pressure of the argon gas, and the electric power level, results in control of partial vaporization of the feedstock to a level such that enough carbon remains to facilitate a continuous line feed.
15. The apparatus of claim 12, wherein the feedstock is selected from the group consisting of a carbon feedstock and a graphite element.
16. The apparatus of claim 12, wherein the feedstock is selected from the group consisting of rod stock and fiber.
17. The apparatus of claim 12, wherein the product formation region is located immediately downstream from the plasma stabilization region.
18. The apparatus of claim 12, wherein the transition metal catalyst and the associated catalyst support comprise a catalyst screen in a deposition nozzle, the catalyst screen being formed from a material that is selected based upon an operating temperature of the plasma stabilization region, wherein the material is selected from the group consisting of ceramic fiber mesh with a transition metallic catalyst coating, a metallic screen made directly from the transition metallic catalyst, a carbon fiber coated with the transition metallic catalyst, and a porous silica membrane with the transition metallic catalyst deposited on an exit side of the membrane.
19. A system for producing single-walled carbon nanotubes, comprising:
a continuous operation, flow-through reactor having an initial region, a plasma stabilization region, and a product formation region;
continuously supplying feedstock to the initial region of the reactor to generate a continuous stream of carbon plasma from the feedstock;
stabilizing the carbon plasma in a vapor phase in the plasma stabilization region with radio frequency energy by controlling a power and a frequency of the radio frequency energy, such that the carbon plasma is stabilized for homogenization of a reactant mixture and transport of a high concentration of the carbon plasma to the product formation region; and
forming a product by depositing the reactant mixture in the product formation region; and
a robotic arm for supporting and manipulating the reactor such that continuous deposition of the product is applied to a workpiece.
20. The system of claim 19, wherein the carbon plasma is stabilized with inductance coils.
21. The system of claim 19, further comprising applying thermal energy inside the reactor to maintain a reactor temperature of approximately 1700° C., such that the thermal energy reduces the radio frequency energy required to stabilize the carbon plasma, and promotes a higher concentration of carbon vapor in the reactor.
22. The system of claim 21, wherein the thermal heat is applied by electrical resistance heaters.
23. The system of claim 19, wherein the carbon plasma is formed by electrical resistance heating of the feedstock, which comprises: continuously feeding the feedstock over two oppositely-charged electrodes while passing low voltage, high current, electric power through the feedstock, such that the feedstock is rapidly resistance-heated, the electric power being regulated by feedback control for measuring a temperature of the feedstock to maintain a peak temperature of approximately 3000° C.; and wherein
the reactor has a reduced pressure inert atmosphere of continuously-flowing gas, and wherein control of a feed rate of the feedstock, the pressure of the gas, and the electric power level, results in control of partial vaporization of the feedstock to a level such that enough carbon remains to facilitate a continuous line feed.
24. The system of claim 19, wherein the product is formed by using a transition metal catalyst and an associated catalyst support in the product formation region.
25. The system of claim 19, wherein the feedstock is selected from the group consisting of carbon feedstock and a graphite element.
26. The system of claim 19, wherein the feedstock is selected from the group consisting of rod stock and fiber.
27. The system of claim 19, wherein the product formation region is located immediately downstream from the plasma stabilization region.
28. The system of claim 19, wherein the product is formed in the product formation region by transporting the stabilized plasma through a catalyst screen in a deposition nozzle, the catalyst screen being formed from a material that is selected based upon an operating temperature of the plasma stabilization region, wherein the material is selected from the group consisting of ceramic fiber mesh with a transition metallic catalyst coating, a metallic screen made directly from the transition metallic catalyst, a carbon fiber coated with the transition metallic catalyst, and a porous silica membrane with the transition metallic catalyst deposited on an exit side of the membrane.
US10/455,767 2003-06-05 2003-06-05 System, method, and apparatus for continuous synthesis of single-walled carbon nanotubes Expired - Fee Related US7261779B2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US10/455,767 US7261779B2 (en) 2003-06-05 2003-06-05 System, method, and apparatus for continuous synthesis of single-walled carbon nanotubes
PCT/US2004/017810 WO2004108591A2 (en) 2003-06-05 2004-06-04 System, method, and apparatus for continuous synthesis of single-walled carbon nanotubes
EP04754421.8A EP1644287B1 (en) 2003-06-05 2004-06-04 Method, and apparatus for continuous synthesis of single-walled carbon nanotubes
US11/834,210 US7763231B2 (en) 2003-06-05 2007-08-06 System and method of synthesizing carbon nanotubes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US10/455,767 US7261779B2 (en) 2003-06-05 2003-06-05 System, method, and apparatus for continuous synthesis of single-walled carbon nanotubes

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/834,210 Division US7763231B2 (en) 2003-06-05 2007-08-06 System and method of synthesizing carbon nanotubes

Publications (2)

Publication Number Publication Date
US20040245088A1 US20040245088A1 (en) 2004-12-09
US7261779B2 true US7261779B2 (en) 2007-08-28

Family

ID=33490014

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/455,767 Expired - Fee Related US7261779B2 (en) 2003-06-05 2003-06-05 System, method, and apparatus for continuous synthesis of single-walled carbon nanotubes
US11/834,210 Expired - Lifetime US7763231B2 (en) 2003-06-05 2007-08-06 System and method of synthesizing carbon nanotubes

Family Applications After (1)

Application Number Title Priority Date Filing Date
US11/834,210 Expired - Lifetime US7763231B2 (en) 2003-06-05 2007-08-06 System and method of synthesizing carbon nanotubes

Country Status (3)

Country Link
US (2) US7261779B2 (en)
EP (1) EP1644287B1 (en)
WO (1) WO2004108591A2 (en)

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100025225A1 (en) * 2003-06-10 2010-02-04 Plasmet Corporation Continuous production of carbon nanomaterials using a high temperature inductively coupled plasma
US20100150815A1 (en) * 2008-12-17 2010-06-17 Alfredo Aguilar Elguezabal Method and apparatus for the continuous production of carbon nanotubes
US20100227058A1 (en) * 2005-12-09 2010-09-09 Tsinghua University Method for fabricating carbon nanotube array
KR101054963B1 (en) * 2008-09-23 2011-08-05 현대하이스코 주식회사 Mold coating method and mobile coating device for same
WO2012037042A1 (en) 2010-09-14 2012-03-22 Applied Nanostructured Solutions, Llc Glass substrates having carbon nanotubes grown thereon and methods for production thereof
US8158217B2 (en) 2007-01-03 2012-04-17 Applied Nanostructured Solutions, Llc CNT-infused fiber and method therefor
US8168291B2 (en) 2009-11-23 2012-05-01 Applied Nanostructured Solutions, Llc Ceramic composite materials containing carbon nanotube-infused fiber materials and methods for production thereof
US8325079B2 (en) 2009-04-24 2012-12-04 Applied Nanostructured Solutions, Llc CNT-based signature control material
US8545963B2 (en) 2009-12-14 2013-10-01 Applied Nanostructured Solutions, Llc Flame-resistant composite materials and articles containing carbon nanotube-infused fiber materials
US8580342B2 (en) 2009-02-27 2013-11-12 Applied Nanostructured Solutions, Llc Low temperature CNT growth using gas-preheat method
US8585934B2 (en) 2009-02-17 2013-11-19 Applied Nanostructured Solutions, Llc Composites comprising carbon nanotubes on fiber
US8601965B2 (en) 2009-11-23 2013-12-10 Applied Nanostructured Solutions, Llc CNT-tailored composite sea-based structures
US8664573B2 (en) 2009-04-27 2014-03-04 Applied Nanostructured Solutions, Llc CNT-based resistive heating for deicing composite structures
US8665581B2 (en) 2010-03-02 2014-03-04 Applied Nanostructured Solutions, Llc Spiral wound electrical devices containing carbon nanotube-infused electrode materials and methods and apparatuses for production thereof
US8780526B2 (en) 2010-06-15 2014-07-15 Applied Nanostructured Solutions, Llc Electrical devices containing carbon nanotube-infused fibers and methods for production thereof
US8787001B2 (en) 2010-03-02 2014-07-22 Applied Nanostructured Solutions, Llc Electrical devices containing carbon nanotube-infused fibers and methods for production thereof
US8815341B2 (en) 2010-09-22 2014-08-26 Applied Nanostructured Solutions, Llc Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof
US8951631B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused metal fiber materials and process therefor
US8951632B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused carbon fiber materials and process therefor
US8969225B2 (en) 2009-08-03 2015-03-03 Applied Nano Structured Soultions, LLC Incorporation of nanoparticles in composite fibers
US8999453B2 (en) 2010-02-02 2015-04-07 Applied Nanostructured Solutions, Llc Carbon nanotube-infused fiber materials containing parallel-aligned carbon nanotubes, methods for production thereof, and composite materials derived therefrom
US9005755B2 (en) 2007-01-03 2015-04-14 Applied Nanostructured Solutions, Llc CNS-infused carbon nanomaterials and process therefor
US9017854B2 (en) 2010-08-30 2015-04-28 Applied Nanostructured Solutions, Llc Structural energy storage assemblies and methods for production thereof
US20150183642A1 (en) * 2011-07-28 2015-07-02 Nanocomp Technologies, Inc. Systems and Methods for Nanoscopically Aligned Carbon Nanotubes
US9085464B2 (en) 2012-03-07 2015-07-21 Applied Nanostructured Solutions, Llc Resistance measurement system and method of using the same
US9111658B2 (en) 2009-04-24 2015-08-18 Applied Nanostructured Solutions, Llc CNS-shielded wires
US9167736B2 (en) 2010-01-15 2015-10-20 Applied Nanostructured Solutions, Llc CNT-infused fiber as a self shielding wire for enhanced power transmission line
US9163354B2 (en) 2010-01-15 2015-10-20 Applied Nanostructured Solutions, Llc CNT-infused fiber as a self shielding wire for enhanced power transmission line
US9506194B2 (en) 2012-09-04 2016-11-29 Ocv Intellectual Capital, Llc Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media
US10029442B2 (en) 2005-07-28 2018-07-24 Nanocomp Technologies, Inc. Systems and methods for formation and harvesting of nanofibrous materials
US10138128B2 (en) 2009-03-03 2018-11-27 Applied Nanostructured Solutions, Llc System and method for surface treatment and barrier coating of fibers for in situ CNT growth

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2385802C (en) 2002-05-09 2008-09-02 Institut National De La Recherche Scientifique Method and apparatus for producing single-wall carbon nanotubes
US7611579B2 (en) * 2004-01-15 2009-11-03 Nanocomp Technologies, Inc. Systems and methods for synthesis of extended length nanostructures
US20060063005A1 (en) * 2004-09-20 2006-03-23 Gardner Slade H Anisotropic carbon alloy having aligned carbon nanotubes
KR101333936B1 (en) 2005-03-04 2013-11-27 노오쓰웨스턴 유니버시티 Separation of carbon nanotubes in density gradients
CA2500766A1 (en) * 2005-03-14 2006-09-14 National Research Council Of Canada Method and apparatus for the continuous production and functionalization of single-walled carbon nanotubes using a high frequency induction plasma torch
JP2010502548A (en) 2006-08-30 2010-01-28 ノースウェスタン ユニバーシティ A population of monodispersed single-walled carbon nanotubes and related methods for providing this population
KR100844456B1 (en) 2006-12-05 2008-07-08 한국전자통신연구원 Manufacturing apparatus and method for carbon nanotubes
BRPI0605767B1 (en) * 2006-12-21 2021-08-10 Universidade Federal Do Pará REACTOR AND PROCESS FOR OBTAINING CARBONous MATERIALS BY SHORT-CIRCUIT CURRENT
US20100279569A1 (en) 2007-01-03 2010-11-04 Lockheed Martin Corporation Cnt-infused glass fiber materials and process therefor
WO2009032090A1 (en) 2007-08-29 2009-03-12 Northwestern University Transparent electrical conductors prepared from sorted carbon nanotubes and methods of preparing same
US9725314B2 (en) * 2008-03-03 2017-08-08 Performancy Polymer Solutions, Inc. Continuous process for the production of carbon nanofiber reinforced continuous fiber preforms and composites made therefrom
US9174847B2 (en) * 2008-05-01 2015-11-03 Honda Motor Co., Ltd. Synthesis of high quality carbon single-walled nanotubes
US20100259752A1 (en) * 2009-04-14 2010-10-14 Lockheed Martin Corporation Sensors with fiber bragg gratings and carbon nanotubes
US20110223343A1 (en) * 2010-03-01 2011-09-15 Auburn University, Office Of Technology Transfer Novel nanocomposite for sustainability of infrastructure
US8753488B2 (en) 2011-06-24 2014-06-17 Jtw, Llc Advanced nano technology for growing metallic nano-clusters
RU2484014C2 (en) * 2011-08-17 2013-06-10 Общество с ограниченной ответственностью "АС и ПП" Method of producing carbon-containing nanoparticles
US20140093728A1 (en) 2012-09-28 2014-04-03 Applied Nanostructured Solutions, Llc Carbon nanostructures and methods of making the same
GB201412656D0 (en) 2014-07-16 2014-08-27 Imp Innovations Ltd Process
US11728477B2 (en) * 2016-07-15 2023-08-15 Oned Material, Inc. Manufacturing apparatus and method for making silicon nanowires on carbon based powders for use in batteries
CN106145089A (en) * 2016-08-31 2016-11-23 无锡东恒新能源科技有限公司 The synthesizer of batch production CNT
WO2018067814A1 (en) 2016-10-06 2018-04-12 Lyten, Inc. Microwave reactor system with gas-solids separation
US9812295B1 (en) 2016-11-15 2017-11-07 Lyten, Inc. Microwave chemical processing
US9767992B1 (en) 2017-02-09 2017-09-19 Lyten, Inc. Microwave chemical processing reactor
US9997334B1 (en) 2017-02-09 2018-06-12 Lyten, Inc. Seedless particles with carbon allotropes
EP3596163A4 (en) 2017-03-16 2021-01-13 Lyten, Inc. Carbon and elastomer integration
US10920035B2 (en) 2017-03-16 2021-02-16 Lyten, Inc. Tuning deformation hysteresis in tires using graphene
US9862606B1 (en) 2017-03-27 2018-01-09 Lyten, Inc. Carbon allotropes
US10465128B2 (en) * 2017-09-20 2019-11-05 Lyten, Inc. Cracking of a process gas
WO2022140416A1 (en) * 2020-12-22 2022-06-30 Nanocomp Technologies, Inc. Two-stage system and method for producing carbon nanotubes
CN117295784A (en) 2021-05-07 2023-12-26 巴斯夫欧洲公司 Polybutylene terephthalate composition and article

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4599133A (en) 1982-05-07 1986-07-08 Hitachi, Ltd. Method of producing single-crystal silicon film
JPH07142198A (en) 1993-11-19 1995-06-02 Ulvac Japan Ltd Plasma source
US5437820A (en) 1992-02-12 1995-08-01 Brotz; Gregory R. Process for manufacturing a three-dimensional shaped product
US5617911A (en) 1995-09-08 1997-04-08 Aeroquip Corporation Method and apparatus for creating a free-form three-dimensional article using a layer-by-layer deposition of a support material and a deposition material
JPH09188509A (en) 1996-01-12 1997-07-22 Nec Corp Production of monolayer carbon manotube
US5718951A (en) 1995-09-08 1998-02-17 Aeroquip Corporation Method and apparatus for creating a free-form three-dimensional article using a layer-by-layer deposition of a molten metal and deposition of a powdered metal as a support material
US5746844A (en) 1995-09-08 1998-05-05 Aeroquip Corporation Method and apparatus for creating a free-form three-dimensional article using a layer-by-layer deposition of molten metal and using a stress-reducing annealing process on the deposited metal
US5787965A (en) 1995-09-08 1998-08-04 Aeroquip Corporation Apparatus for creating a free-form metal three-dimensional article using a layer-by-layer deposition of a molten metal in an evacuation chamber with inert environment
US5837960A (en) 1995-08-14 1998-11-17 The Regents Of The University Of California Laser production of articles from powders
US5998097A (en) 1994-10-18 1999-12-07 Ebara Corporation Fabrication method employing energy beam source
US6046426A (en) 1996-07-08 2000-04-04 Sandia Corporation Method and system for producing complex-shape objects
US6183714B1 (en) * 1995-09-08 2001-02-06 Rice University Method of making ropes of single-wall carbon nanotubes
US6268584B1 (en) 1998-01-22 2001-07-31 Optomec Design Company Multiple beams and nozzles to increase deposition rate
WO2002000963A1 (en) 2000-06-23 2002-01-03 Steven John Ouderkirk Selective beam deposition
US20020090331A1 (en) 1997-03-07 2002-07-11 William Marsh Rice University Method for growing continuous fiber
US6761870B1 (en) * 1998-11-03 2004-07-13 William Marsh Rice University Gas-phase nucleation and growth of single-wall carbon nanotubes from high pressure CO
US20060127299A1 (en) * 2002-11-15 2006-06-15 Mcgill University Method for producing carbon nanotubes using a dc non-transferred thermal plasma torch

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US150524A (en) * 1874-05-05 Improvement in plow-beams
US127169A (en) * 1872-05-28 Improvement in torsion-springs for vehicles
US159943A (en) * 1875-02-16 Improvement in ticket-reels
US90330A (en) * 1869-05-18 Improved reversible hinge
US102196A (en) * 1870-04-19 Improvement in advertising-desks
US90331A (en) * 1869-05-18 corse
US136683A (en) * 1873-03-11 Improvement in fastenings for railroad-rail joints
US94311A (en) * 1869-08-31 Improvement in churns
US98135A (en) * 1869-12-21 Improvement in machine tor spinning and curling hair
US127162A (en) * 1872-05-28 Improvement in gas apparatus for melting snow and ice on sidewalks
US136681A (en) * 1873-03-11 Improvement in sash-holders
JPS59180519A (en) 1983-03-31 1984-10-13 Hitachi Ltd Vapor-phase film forming device of coherence reduced laser
US4924807A (en) * 1986-07-26 1990-05-15 Nihon Shinku Gijutsu Kabushiki Kaisha Apparatus for chemical vapor deposition
US4778693A (en) * 1986-10-17 1988-10-18 Quantronix Corporation Photolithographic mask repair system
US4801352A (en) * 1986-12-30 1989-01-31 Image Micro Systems, Inc. Flowing gas seal enclosure for processing workpiece surface with controlled gas environment and intense laser irradiation
US5060595A (en) * 1988-04-12 1991-10-29 Ziv Alan R Via filling by selective laser chemical vapor deposition
US5171610A (en) * 1990-08-28 1992-12-15 The Regents Of The University Of Calif. Low temperature photochemical vapor deposition of alloy and mixed metal oxide films
US5145714A (en) * 1990-10-30 1992-09-08 Mcnc Metal-organic chemical vapor deposition for repairing broken lines in microelectronic packages
JPH052152A (en) * 1990-12-19 1993-01-08 Hitachi Ltd Method and device for light beam generation, method for size measurement, outward shape inspection, height measurement, and exposure using same, and manufacture of semiconductor integrated circuit device
FR2685127B1 (en) * 1991-12-13 1994-02-04 Christian Licoppe GAS PHOTONANOGRAPH FOR THE MANUFACTURE AND OPTICAL ANALYSIS OF PATTERNS ON THE NANOMETRIC SCALE.
US5745153A (en) * 1992-12-07 1998-04-28 Eastman Kodak Company Optical means for using diode laser arrays in laser multibeam printers and recorders
JP3212755B2 (en) * 1993-05-19 2001-09-25 株式会社東芝 Method for producing needle-like substance and method for producing micro-emitter array
US6033721A (en) * 1994-10-26 2000-03-07 Revise, Inc. Image-based three-axis positioner for laser direct write microchemical reaction
KR0158780B1 (en) * 1994-12-22 1998-11-16 가네꼬 히사시 Method and apparatus for film formation by chemical vapor deposition
US5779863A (en) * 1997-01-16 1998-07-14 Air Liquide America Corporation Perfluorocompound separation and purification method and system
US5963577A (en) * 1997-04-11 1999-10-05 Blue Sky Research Multiple element laser diode assembly incorporating a cylindrical microlens
US6777045B2 (en) * 2001-06-27 2004-08-17 Applied Materials Inc. Chamber components having textured surfaces and method of manufacture

Patent Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4599133A (en) 1982-05-07 1986-07-08 Hitachi, Ltd. Method of producing single-crystal silicon film
US5437820A (en) 1992-02-12 1995-08-01 Brotz; Gregory R. Process for manufacturing a three-dimensional shaped product
JPH07142198A (en) 1993-11-19 1995-06-02 Ulvac Japan Ltd Plasma source
US5998097A (en) 1994-10-18 1999-12-07 Ebara Corporation Fabrication method employing energy beam source
US5837960A (en) 1995-08-14 1998-11-17 The Regents Of The University Of California Laser production of articles from powders
US5746844A (en) 1995-09-08 1998-05-05 Aeroquip Corporation Method and apparatus for creating a free-form three-dimensional article using a layer-by-layer deposition of molten metal and using a stress-reducing annealing process on the deposited metal
US5718951A (en) 1995-09-08 1998-02-17 Aeroquip Corporation Method and apparatus for creating a free-form three-dimensional article using a layer-by-layer deposition of a molten metal and deposition of a powdered metal as a support material
US5787965A (en) 1995-09-08 1998-08-04 Aeroquip Corporation Apparatus for creating a free-form metal three-dimensional article using a layer-by-layer deposition of a molten metal in an evacuation chamber with inert environment
US5960853A (en) 1995-09-08 1999-10-05 Aeroquip Corporation Apparatus for creating a free-form three-dimensional article using a layer-by-layer deposition of a molten metal and deposition of a powdered metal as a support material
US5617911A (en) 1995-09-08 1997-04-08 Aeroquip Corporation Method and apparatus for creating a free-form three-dimensional article using a layer-by-layer deposition of a support material and a deposition material
US6183714B1 (en) * 1995-09-08 2001-02-06 Rice University Method of making ropes of single-wall carbon nanotubes
JPH09188509A (en) 1996-01-12 1997-07-22 Nec Corp Production of monolayer carbon manotube
US6046426A (en) 1996-07-08 2000-04-04 Sandia Corporation Method and system for producing complex-shape objects
US20020127169A1 (en) 1997-03-07 2002-09-12 William Marsh Rice University Method for purification of as-produced single-wall carbon nanotubes
US20020127162A1 (en) 1997-03-07 2002-09-12 William Marsh Rice University Continuous fiber of single-wall carbon nanotubes
US20020090331A1 (en) 1997-03-07 2002-07-11 William Marsh Rice University Method for growing continuous fiber
US20020090330A1 (en) 1997-03-07 2002-07-11 William Marsh Rice University Method for growing single-wall carbon nanotubes utlizing seed molecules
US20020094311A1 (en) 1997-03-07 2002-07-18 William Marsh Rice University Method for cutting nanotubes
US20020098135A1 (en) 1997-03-07 2002-07-25 William Marsh Rice University Array of single-wall carbon nanotubes
US20020102196A1 (en) 1997-03-07 2002-08-01 William Marsh Rice University Compositions and articles of manufacture
US20020159943A1 (en) 1997-03-07 2002-10-31 William Marsh Rice University Method for forming an array of single-wall carbon nanotubes and compositions thereof
US20020150524A1 (en) 1997-03-07 2002-10-17 William Marsh Rice University Methods for producing composites of single-wall carbon nanotubes and compositions thereof
US20020136683A1 (en) 1997-03-07 2002-09-26 William Marsh Rice University Method for forming composites of sub-arrays of single-wall carbon nanotubes
US20020136681A1 (en) 1997-03-07 2002-09-26 William Marsh Rice University Method for producing a catalyst support and compositions thereof
US6268584B1 (en) 1998-01-22 2001-07-31 Optomec Design Company Multiple beams and nozzles to increase deposition rate
US6761870B1 (en) * 1998-11-03 2004-07-13 William Marsh Rice University Gas-phase nucleation and growth of single-wall carbon nanotubes from high pressure CO
WO2002000963A1 (en) 2000-06-23 2002-01-03 Steven John Ouderkirk Selective beam deposition
US20060127299A1 (en) * 2002-11-15 2006-06-15 Mcgill University Method for producing carbon nanotubes using a dc non-transferred thermal plasma torch

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
Database WPI, Derwent Publications Ltd., London; Section Ch, Week 199739.
Lange H, et al. An Optoelectronic Control of Arc Gap During Formation of Fullerenes and Carbon Nanotubes, Review of Scientific Instruments AIP USA, vol. 68, No. 10, Oct. 1997, pp. 3723-3727.
Li et al., Large Scale Synthesis of Aligned Carbon Nanotubes, Dec. 6, 1996, Science Magazine, vol. 274, pp. 1701-1703. *
Smiljanic O, et al. Gas-Phase Synthesis of SWNT by an Atmospheric Pressure Plasma Jet, and Chemical Physics Letters, North-Holland, Amsterdam, NL, vol. 356, Apr. 22, 2002, pp. 189-193.
Yoshida et al., Characterization of hybrid plasma and its application to a chemical synthesis, Feb. 1983, Journal of Applied Physics, vol. 54, Issue 2, pp. 640-646. *
Yoshie et al., Novel Method for C60 synthesis: A thermal plasma at atmospheric pressure, Dec. 7, 1992, Applied Physics Letters, vol. 61, No. 23, pp. 2782-2783.□□ *

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100025225A1 (en) * 2003-06-10 2010-02-04 Plasmet Corporation Continuous production of carbon nanomaterials using a high temperature inductively coupled plasma
US10029442B2 (en) 2005-07-28 2018-07-24 Nanocomp Technologies, Inc. Systems and methods for formation and harvesting of nanofibrous materials
US20100227058A1 (en) * 2005-12-09 2010-09-09 Tsinghua University Method for fabricating carbon nanotube array
US8158217B2 (en) 2007-01-03 2012-04-17 Applied Nanostructured Solutions, Llc CNT-infused fiber and method therefor
US9574300B2 (en) 2007-01-03 2017-02-21 Applied Nanostructured Solutions, Llc CNT-infused carbon fiber materials and process therefor
US9573812B2 (en) 2007-01-03 2017-02-21 Applied Nanostructured Solutions, Llc CNT-infused metal fiber materials and process therefor
US8951631B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused metal fiber materials and process therefor
US9005755B2 (en) 2007-01-03 2015-04-14 Applied Nanostructured Solutions, Llc CNS-infused carbon nanomaterials and process therefor
US8951632B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused carbon fiber materials and process therefor
KR101054963B1 (en) * 2008-09-23 2011-08-05 현대하이스코 주식회사 Mold coating method and mobile coating device for same
US8119074B2 (en) 2008-12-17 2012-02-21 Centro de Investigacion en Materiales Avanzados, S.C Method and apparatus for the continuous production of carbon nanotubes
US20100150815A1 (en) * 2008-12-17 2010-06-17 Alfredo Aguilar Elguezabal Method and apparatus for the continuous production of carbon nanotubes
US8585934B2 (en) 2009-02-17 2013-11-19 Applied Nanostructured Solutions, Llc Composites comprising carbon nanotubes on fiber
US8580342B2 (en) 2009-02-27 2013-11-12 Applied Nanostructured Solutions, Llc Low temperature CNT growth using gas-preheat method
US10138128B2 (en) 2009-03-03 2018-11-27 Applied Nanostructured Solutions, Llc System and method for surface treatment and barrier coating of fibers for in situ CNT growth
US8325079B2 (en) 2009-04-24 2012-12-04 Applied Nanostructured Solutions, Llc CNT-based signature control material
US9111658B2 (en) 2009-04-24 2015-08-18 Applied Nanostructured Solutions, Llc CNS-shielded wires
US9241433B2 (en) 2009-04-24 2016-01-19 Applied Nanostructured Solutions, Llc CNT-infused EMI shielding composite and coating
US8664573B2 (en) 2009-04-27 2014-03-04 Applied Nanostructured Solutions, Llc CNT-based resistive heating for deicing composite structures
US8969225B2 (en) 2009-08-03 2015-03-03 Applied Nano Structured Soultions, LLC Incorporation of nanoparticles in composite fibers
US8662449B2 (en) 2009-11-23 2014-03-04 Applied Nanostructured Solutions, Llc CNT-tailored composite air-based structures
US8601965B2 (en) 2009-11-23 2013-12-10 Applied Nanostructured Solutions, Llc CNT-tailored composite sea-based structures
US8168291B2 (en) 2009-11-23 2012-05-01 Applied Nanostructured Solutions, Llc Ceramic composite materials containing carbon nanotube-infused fiber materials and methods for production thereof
US8545963B2 (en) 2009-12-14 2013-10-01 Applied Nanostructured Solutions, Llc Flame-resistant composite materials and articles containing carbon nanotube-infused fiber materials
US9163354B2 (en) 2010-01-15 2015-10-20 Applied Nanostructured Solutions, Llc CNT-infused fiber as a self shielding wire for enhanced power transmission line
US9167736B2 (en) 2010-01-15 2015-10-20 Applied Nanostructured Solutions, Llc CNT-infused fiber as a self shielding wire for enhanced power transmission line
US8999453B2 (en) 2010-02-02 2015-04-07 Applied Nanostructured Solutions, Llc Carbon nanotube-infused fiber materials containing parallel-aligned carbon nanotubes, methods for production thereof, and composite materials derived therefrom
US8787001B2 (en) 2010-03-02 2014-07-22 Applied Nanostructured Solutions, Llc Electrical devices containing carbon nanotube-infused fibers and methods for production thereof
US8665581B2 (en) 2010-03-02 2014-03-04 Applied Nanostructured Solutions, Llc Spiral wound electrical devices containing carbon nanotube-infused electrode materials and methods and apparatuses for production thereof
US8780526B2 (en) 2010-06-15 2014-07-15 Applied Nanostructured Solutions, Llc Electrical devices containing carbon nanotube-infused fibers and methods for production thereof
US9017854B2 (en) 2010-08-30 2015-04-28 Applied Nanostructured Solutions, Llc Structural energy storage assemblies and methods for production thereof
US9907174B2 (en) 2010-08-30 2018-02-27 Applied Nanostructured Solutions, Llc Structural energy storage assemblies and methods for production thereof
US8784937B2 (en) 2010-09-14 2014-07-22 Applied Nanostructured Solutions, Llc Glass substrates having carbon nanotubes grown thereon and methods for production thereof
WO2012037042A1 (en) 2010-09-14 2012-03-22 Applied Nanostructured Solutions, Llc Glass substrates having carbon nanotubes grown thereon and methods for production thereof
US8815341B2 (en) 2010-09-22 2014-08-26 Applied Nanostructured Solutions, Llc Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof
US20150183642A1 (en) * 2011-07-28 2015-07-02 Nanocomp Technologies, Inc. Systems and Methods for Nanoscopically Aligned Carbon Nanotubes
US9085464B2 (en) 2012-03-07 2015-07-21 Applied Nanostructured Solutions, Llc Resistance measurement system and method of using the same
US9506194B2 (en) 2012-09-04 2016-11-29 Ocv Intellectual Capital, Llc Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media

Also Published As

Publication number Publication date
EP1644287A2 (en) 2006-04-12
WO2004108591A2 (en) 2004-12-16
WO2004108591A3 (en) 2005-08-18
US20080170983A1 (en) 2008-07-17
EP1644287B1 (en) 2014-12-24
US7763231B2 (en) 2010-07-27
US20040245088A1 (en) 2004-12-09

Similar Documents

Publication Publication Date Title
US7261779B2 (en) System, method, and apparatus for continuous synthesis of single-walled carbon nanotubes
US7824649B2 (en) Apparatus and method for synthesizing a single-wall carbon nanotube array
US7097906B2 (en) Pure carbon isotropic alloy of allotropic forms of carbon including single-walled carbon nanotubes and diamond-like carbon
US20060185595A1 (en) Apparatus and process for carbon nanotube growth
US7056479B2 (en) Process for preparing carbon nanotubes
US6884404B2 (en) Method of manufacturing carbon nanotubes and/or fullerenes, and manufacturing apparatus for the same
US7033650B2 (en) Method of producing a nanotube layer on a substrate
US20050260412A1 (en) System, method, and apparatus for producing high efficiency heat transfer device with carbon nanotubes
US9776865B2 (en) Induction-coupled plasma synthesis of boron nitride nanotubes
US11923176B2 (en) Temperature-controlled chemical processing reactor
KR20030028296A (en) Plasma enhanced chemical vapor deposition apparatus and method of producing a cabon nanotube using the same
WO2008094465A1 (en) Synthesis of carbon nanotubes by selectively heating catalyst
US20050287297A1 (en) Apparatus and methods of making nanostructures by inductive heating
US7306503B2 (en) Method and apparatus of fixing carbon fibers on a substrate using an aerosol deposition process
Liu et al. Advances of microwave plasma-enhanced chemical vapor deposition in fabrication of carbon nanotubes: a review
RU2455119C2 (en) Method to produce nanoparticles
US7125525B2 (en) Device and method for production of carbon nanotubes, fullerene and their derivatives
CN100515935C (en) Carbon nano-tube growth apparatus and method
Harbec et al. Carbon nanotubes from the dissociation of C2Cl4 using a dc thermal plasma torch
Jašek et al. Synthesis of carbon nanostructures by plasma enhanced chemical vapour deposition at atmospheric pressure
JP4665113B2 (en) Fine particle production method and fine particle production apparatus
JP2003238124A (en) Method for manufacturing carbon nanotube
Gowrisankar et al. Large-Scale Continuous Production of Carbon Nanotubes-A Review
WO2022046296A1 (en) Temperature-controlled chemical processing reactor
JP2011063468A (en) Process for producing single wall carbon nanotube

Legal Events

Date Code Title Description
AS Assignment

Owner name: LOCKHEED MARTIN CORPORATION, TEXAS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GARDNER, SLADE H.;REEL/FRAME:014161/0642

Effective date: 20030528

AS Assignment

Owner name: LOCKHEED MARTIN CORPORATION, MARYLAND

Free format text: RE-RECORD TO CORRECT THE ADDRESS OF THE ASSIGNEE, PREVIOUSLY RECORDED ON REEL 014161 FRAME 0642.;ASSIGNOR:GARDNER, SLADE H.;REEL/FRAME:014799/0373

Effective date: 20030528

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FEPP Fee payment procedure

Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

LAPS Lapse for failure to pay maintenance fees

Free format text: PATENT EXPIRED FOR FAILURE TO PAY MAINTENANCE FEES (ORIGINAL EVENT CODE: EXP.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20190828